ELTE  Institute of Chemistry, ELTE

Title: Analysis of Kinetic Reaction Mechanisms
Neptun codes: kv2n9p60, KÉM/083E, KÉM/283
Course: Chemistry BSc/MSc, chemistry teacher, PhD students
Number of lectures: 2 hours lectures / week
Lecture: Tamás Turányi, Professor of Chemistry
e-mail: turanyi@chem.elte.hu
Chemistry, Office 146
Exam: oral exam
Type: special course

Dates and times of the lectures in 2017:   TBA

Exam dates

2016.12.19. 9:30    room 065
2017.01.05. 9:30    room 065  
2017.01.12. 9:30    room 065  
2017.01.17. 9:30    room 065

2017.01.23. 9:30    room 065     repeated exam only

Chemical processes in many fields of science and technology, including combustion, atmospheric chemistry, environmental modelling, process engineering, and systems biology, can be described by detailed reaction mechanisms consisting of numerous reaction steps. This book describes methods that are applicable in all these fields. Topics addressed include: how sensitivity and uncertainty analyses allow the calculation of the overall uncertainty of simulation results and the identification of the most important input parameters, the ways in which mechanisms can be reduced without losing important kinetic and dynamic detail, and the application of reduced models for more accurate engineering optimizations. This monograph is invaluable for researchers and engineers dealing with detailed reaction mechanisms, but is also useful for graduate students of related courses in chemistry, mechanical engineering, energy and environmental science and biology.

Topics of the lectures:

1. Reaction kinetics basics
stoichiometry and reaction rate, temperature and pressure parameterisation of the rate coefficients, basic simplification principles in reaction kinetics, mechanism construction and the sources of data, reaction pathway analysis, main applications of reaction kinetics

2. Local sensitivity analysis
local sensitivity coefficients, brute force method, Green function method, decoupled direct method, automatic differentiation, principal component analysis of the sensitivity matrix, local uncertainty analysis

3. Global uncertainty analysis
Morris’ screening method, global uncertainty analysis using sampling based methods, Fourier Amplitude Sensitivity Test (FAST), sensitivity indices, Response Surface Methods (RSMs), uncertainty analysis: general conclusions

4. Uncertainty analysis of reaction kinetic models
uncertainty of thermodynamic data and rate coefficients, local uncertainty analysis of reaction kinetic models, prior and posterior uncertainties of chemical kinetic data, uncertainty of the Arrhenius parameters

5. Time-scale analysis
species lifetimes and time-scales, application of perturbation theory to chemical kinetic systems, computational singular perturbation (CSP) theory, slow manifolds in the space of variables, time-scales in reactive flow models, stiffness of reaction kinetic models, operator splitting and stiffness

6. Reduction of reaction mechanisms without time scale analysis
identification of redundant reaction steps using rate-of-production and sensitivity methods

Reduction of reaction mechanisms via finding redundant species
species elimination via trial and error, connectivity method: connections between the species defined by the Jacobian, Simulation Error Minimization Connectivity Method (SEM-CM), graph based methods (DRG, DRG-ASA, DRGEP, FPA), species lumping

8. Reduction of reaction mechanisms based on time scale analysis
quasi-steady-state approximation (QSSA), CSP-based mechanism reduction, slow manifold methods, intrinsic low-dimensional manifolds (ILDMs), tabulation approaches, numerical reduced models based on fitting

9. Similarity of sensitivity functions
origins of local similarity and scaling relationships, origin of global similarity, similarity of the sensitivity functions of biological models, importance of the similarity of sensitivity functions

10. Computer codes for the study of complex reaction systems
general simulation codes in reaction kinetics, simulation of gas kinetics systems, analysis of reaction mechanisms, investigation of biological reaction kinetic systems, codes for global uncertainty analysis

Recommended reading:

Tamás Turányi, Alison S. Tomlin:
Analysis of kinetic reaction mechanisms
Springer, 2014

PowerPoint file of the lectures (7.2 Mbyte, in pdf handout format, last updated 19 October, 2016)

Exam topics

 Edited by Tamás Turányi.